EP3442728B1 - Poudre de cermet ou de carbure cémenté et impression tridimensionnelle en utilisant ce poudre - Google Patents

Poudre de cermet ou de carbure cémenté et impression tridimensionnelle en utilisant ce poudre Download PDF

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Publication number
EP3442728B1
EP3442728B1 EP16805772.7A EP16805772A EP3442728B1 EP 3442728 B1 EP3442728 B1 EP 3442728B1 EP 16805772 A EP16805772 A EP 16805772A EP 3442728 B1 EP3442728 B1 EP 3442728B1
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Prior art keywords
powder
cermet
cemented carbide
particles
printing
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German (de)
English (en)
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EP3442728A1 (fr
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John DE FLON
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • B23B27/148—Composition of the cutting inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C5/00—Milling-cutters
    • B23C5/16—Milling-cutters characterised by physical features other than shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/008—Abrasive bodies without external bonding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B10/00—Drill bits
    • E21B10/46—Drill bits characterised by wear resisting parts, e.g. diamond inserts
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21C—MINING OR QUARRYING
    • E21C35/00—Details of, or accessories for, machines for slitting or completely freeing the mineral from the seam, not provided for in groups E21C25/00 - E21C33/00, E21C37/00 or E21C39/00
    • E21C35/18—Mining picks; Holders therefor
    • E21C35/183—Mining picks; Holders therefor with inserts or layers of wear-resisting material
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21C—MINING OR QUARRYING
    • E21C35/00—Details of, or accessories for, machines for slitting or completely freeing the mineral from the seam, not provided for in groups E21C25/00 - E21C33/00, E21C37/00 or E21C39/00
    • E21C35/18—Mining picks; Holders therefor
    • E21C35/183—Mining picks; Holders therefor with inserts or layers of wear-resisting material
    • E21C35/1835—Chemical composition or specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/66—Treatment of workpieces or articles after build-up by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2207/00—Aspects of the compositions, gradients
    • B22F2207/01—Composition gradients
    • B22F2207/03—Composition gradients of the metallic binder phase in cermets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/10—Carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
    • B23B2222/16—Cermet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23C—MILLING
    • B23C2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
    • B23C2222/16—Cermet
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present invention relates to a method of three dimensional printing of a cermet or cemented carbide body.
  • the present invention also relates to a powder to be used in three dimensional printing.
  • the powder comprises cermet and/or cemented carbide powder wherein 30-70 vol% of the powder particles are ⁇ 10 ⁇ m in diameter and wherein the particles with a diameter of > 20 ⁇ m are porous.
  • Three dimensional (3D) printing or additive manufacturing is a promising manufacturing technique that makes it possible to print a three dimensional body.
  • a model of the body is typically created in a computer program and this model is then printed in a three dimensional printing machine or apparatus.
  • Three dimensional printing is a promising manufacturing technique because it makes it possible to produce complex structures and bodies that cannot be achieved via conventional manufacturing processes.
  • One type of three dimensional printing is based on binder jetting wherein an ink jet type printer head is used to spray binder onto a thin layer of powder, which, when set, forms a sheet of glued together powder for a given layer of an object. After the binder is set, a next thin layer of powder is spread over the original layer, and the printed jetting of binder is repeated in the pattern for that layer. The powder that was not printed with the binder remains where it was originally deposited and serves as a foundation and as support for the printed structure. When printing of the object is complete, the binder is cured at an increased temperature and subsequently the powder not printed with binder is removed by for example an air stream or brushing.
  • Cermet and cemented carbide materials consist of hard constituents of carbides and/or nitrides such as WC or TiC in a metallic binder phase of for example Co. These materials are useful in high demanding applications due to their high hardness and high wear resistance in combination with a high toughness. Examples of areas of application are cutting tools for metal cutting, drill bits for rock drilling and wear parts.
  • Three dimensional printing of tungsten carbide-10 wt% cobalt using cobalt oxide precursor by Kernan et al, International Journal of Refractory Metals and Hard Materials 25 (2007), p. 82-94 , discloses a slurry-based three dimensional printing of cemented carbide insert using cobalt oxide that is reduced into cobalt metal during a sintering step.
  • WO2015/073081A1 relates to additive manufacturing of granular composites of the materials metallic, ceramic, cermet, polymer, plastic, glass-metal and glass-plastic mixtures.
  • the disclosure relates to granular composite density enhancement and particle volumes and particle porosity the are defined.
  • EP2690196A1 discloses a method for treating a Cu thin sheet.
  • the method comprises steps of supplying a slurry in which a diffusion bonding aid and a reinforcing material are dispersed in a solvent on a Cu thin sheet, drying the supplied slurry, and applying a laser to induce melting, solidification, and fixation, so as to form a buildup layer.
  • a Ni or Ni-Cr alloy powder is used as the diffusion bonding aid
  • a carbide base metal compound, a nitride base metal compound, or a boride base metal compound is used as the reinforcing material.
  • the distribution ratio D90/D10 of the diffusion bonding aid and the distribution ratio D90/D10 of the reinforcing material are defined.
  • JP2002356328A discloses fine niobium oxide powder produced by a drying treatment of a slurry. In the powder a ratio of particle diameter distribution D90/D10 is defined.
  • WO2015/162206A2 discloses a method of making a powder of dense and spherically shaped cemented carbide or cermet granules and it also relates to a powder produced by the method and use of said powder in additive manufacturing such as 3D printing by the binder jetting technique.
  • the present invention relates to a powder for three dimensional printing of a cermet or cemented carbide body, wherein said powder comprises cemented carbide and/or cermet particles with a D90 of 15-35 ⁇ m, preferably 17-30 ⁇ m, and wherein the average porosity of the cermet and/or cemented carbide particles with a diameter of ⁇ 20 ⁇ m is 10-40 vol%, preferably 15-30 vol%, more preferably 20-25 vol%, and wherein 30-70 vol% or 30-65 vol%, preferably 40-65 or 45-65 vol%, of the particles are ⁇ 10 ⁇ m in diameter.
  • the powder of the present invention has shown advantages in that three dimensional bodies of cermet or cemented carbide can be printed successfully with satisfying properties relating to porosity and/or metallic binder phase enriched zones. It has been found that the combination of sufficient particle porosity and an adapted particle size distribution is important for the final density and homogeneity of the cermet or cemented carbide body.
  • An average porosity in the larger particles of 10-40 vol%, or 15-30 vol%, or 17-30 vol% or 15-25 vol% is advantageous in adding sintering activity to the three dimensional printed green body.
  • the porosity in particles contributes to the sintering activity during the sintering of the printed green body. If the porosity of the particles is too low the sintering activity in the green body during sintering will be reduced and residual porosity and/or open porosity might appear after the sintering step.
  • the porosity is preferably adjusted based on the binder phase content. A lower binder phase content generally requires a higher porosity of the cermet or cemented carbide particles to provide sufficient sintering activity.
  • the porosity can for example be measured in a LOM at 1000x magnification.
  • the green body will be relatively fragile. The reason to causing the green body to be fragile is probably that capillary forces cause a sucking up of printing binder into the porous particles, leaving less printing binder at the surface of each porous particle and thereby causing a weaker connection between particles.
  • the green strength of the printed green body can be increased to a sufficient level if the powder comprises particles of a selected particle distribution. If the powder comprises more than 70 vol% particles with a diameter ⁇ 10 ⁇ m, the flow of the powder during printing will be uneven and demanding. If the amount of these ⁇ 10 ⁇ m particles is lower than 30 wt% the green strength of the printed green body will be insufficient. Fine particles also contribute in sintering activity and thereby contribute to reduced residual porosity. The fine ⁇ 10 ⁇ m particles contribute with an increased printing binder (glue) locking of the powder during the printing so that the green strength become sufficient.
  • the cemented carbide and/or cermet particles of the powder of the present invention comprise a relatively high fraction of fine particles. These fine particles are milled to its fine size and the milling also implies that the fine particles are irregular in shape, i.e. they are typically not spherical. An advantage with these particles is that the powder bed formed during printing is stable.
  • the three dimensional printing of a cermet or cemented carbide body may result in a body of any shape suitable for its purpose.
  • Cermet and the cemented carbide both comprise hard constituents in a metallic binder phase.
  • cemented carbide at least a portion of the hard constituents consists of WC.
  • the number and size of pores in the three dimensional printed and sintered cermet or cemented carbide body is preferably lower than A06 and/or B06 as defined in ISO4505-1978, preferably lower than A04 and/or B04 more preferably lower than A02 and/or B02.
  • the number and size of pores in the three dimensional printed and sintered cermet or cemented carbide body is preferably lower than A02B00C00, A00B02C00 or A02B02C00. Most preferably no pores are present in the three dimensional printed and sintered cermet or cemented carbide body.
  • the D90 of the porous particles is 15-35 ⁇ m, preferably 17-30 ⁇ m. This is advantageous in that it provides a powder with good flow during printing and decreased risk for problems related to metallic binder phase enriched zones. Too large porous particles tend to contribute in the formation of metallic binder phase enriched zones in the sintered cermet or cemented carbide body.
  • the sintered cermet or cemented carbide body ideally consists of a material composed of hard constituents such as WC in a metallic binder phase such as Co, wherein the metallic binder phase is evenly or homogeneously distributed inside the body and wherein any metallic binder phase enriched zones homogeneously or evenly distributed.
  • the D50 of the cemented carbide and/or cermet particles is 5-20 ⁇ m, preferably 7-15 ⁇ m, more preferably 9-13 ⁇ m.
  • the D10 of the cemented carbide and/or cermet particles is 1-5 ⁇ m.
  • the particle size distribution of the cemented carbide and/or cermet particles in the powder is unimodal. This is advantageous in that the powder can be milled to reach a preferred particle size distribution.
  • the cermet and/or cemented carbide particles comprise a metallic binder phase and wherein the average content of metallic binder phase in the powder is 8-14 wt%, preferably 9-13 wt% or 10-13 wt%.
  • the metallic binder phase content is herein calculated excluding the organic binder, based on only hard constituents and metallic binder content in powder.
  • a metallic binder phase content within this range is advantageous in that the density of pores in the sintered cermet or cemented carbide body may be very limited and still the body can gain from the hardness and toughness that is characteristic for a cermet or cemented carbide body.
  • the cermet or cemented carbide also typically comprises hard constituents. These hard constituents are ceramic and can for example be TiN, TiCN, TiC and/or WC in any combination.
  • the metallic binder phase content is 8-11 wt% and 50-70 vol% of the cermet or cemented carbide particles are ⁇ 10 ⁇ m in diameter.
  • the metallic binder phase content is 11-14 wt% and 35-50 vol % of the cermet or cemented carbide particles are ⁇ 10 ⁇ m in diameter.
  • the cermet and/or cemented carbide particles comprise a metallic binder phase and said metallic binder phase comprises Co.
  • the metallic binder phase comprises more than 90 wt% Co.
  • the metallic binder phase consists of Co.
  • the cemented carbide particles comprises WC and wherein the average WC grain size is 0.5-5 ⁇ m or 0.5-2 ⁇ m. Preferably more than 90 wt% of the hard constituents are WC.
  • the present invention also relates to a method of making a 3D printed cermet or cemented carbide body, said method comprising the steps of:
  • the method further comprise, subsequent to 3D printing and before sintering, the steps of:
  • Curing is normally performed as a part of the printing step.
  • the printing binder is cured whereby the green body gets a sufficient green strength.
  • the curing can be performed by subjecting the printed green body to an increased temperature, such as 150-250 °C before removal of the excessive powder.
  • the curing is performed in a non-oxidation environment such as in Ar or N 2 .
  • the sintering step comprises a debinding step, where the printing binder is burned off.
  • the printing binder comprises a solvent that partly evaporates during the printing.
  • the printing binder can be water-based.
  • the spray dried powder is sieved before the pre-sintering step, preferably sieved to remove particles larger than 42 ⁇ m in diameter. This is advantageous in that it reduces the risk of problems with very large particles in the powder.
  • the three dimensional printing is performed in a three dimensional printing machine such as a binder jet three dimensional printing machine.
  • the sintering is performed in a sintering furnace.
  • the method further comprise a step of, subsequent to or integrated into the sintering step, a step of so called sinter-HIP or GPS (gas pressure sintering) the cermet or cemented carbide body.
  • the sinter-HIP may be performed at a temperature of 1300-1500°C.
  • the sinter-HIP may be performed at a pressure of 20-100 bar.
  • a pressure is applied.
  • the aim of the sinter-HIP step is to reduce any porosity left after the sintering by densifying the material. Any closed porosity in the sintered body is encapsulated and the applied pressure will reduce the porosity. Open porosity can on the other hand not be reduced using sinter-HIP.
  • the three dimensional printing is a binder jetting.
  • Binder jetting is advantageous in that it is a relatively cheap three dimensional printing method.
  • a step of grinding or polishing the body can be added as a final step after the sintering step.
  • the 3D printed body is a cutting tool for metal cutting or a cutting tool for mining application or a wear part.
  • a further disclosure, not part of the invention, relates to the use of said powder in three dimensional printing of a cutting tool for metallic cutting such as an insert, a drill or an end mill, or a cutting tool for mining application such as a drill bit, or a wear part.
  • a further disclosure not part of the invention, also relates to a 3D printed cermet or cemented carbide body with a microstructure of the classification A00B00C00.
  • the 3D printed cermet or cemented carbide body is composed of hard constituents in a binder phase wherein the binder phase content is varying in the body such that a binder phase content measurement in a direction perpendicular from at least one surface of the body towards the center of the body shows a binder phase content variation being periodically with a period P, wherein the period P is 40-140 ⁇ m.
  • the periodicity typically originates from the layered printing process.
  • the average binder phase content shows, as an average of 15 adjacent periods, a difference of 10-20% from the average binder phase content in the body.
  • the average binder phase content shows, as an average of 15 adjacent periods, a difference of 10-50% from the average binder phase content in the body.
  • the average metallic binder phase content in the body is 8-14 wt%.
  • the metallic binder phase comprises Co.
  • the hard constituents comprises WC, preferably with an average WC grain size of 0.5-5 ⁇ m.
  • the body is a cutting tool for metal cutting or a wear part.
  • the metallic binder phase content variation can for example be measured by WDS (Wavelength-dispersive X-ray spectroscopy) or EDS (Energy-dispersive X-ray spectroscopy). Since the cermet or cemented carbide body is a composite comprising a metallic binder phase and hard constituents the binder phase content has to be measured as an average. The area needed to give a value of the binder phase content is to be selected by the skilled person but can for example be a scan width of 200 ⁇ m.
  • the periodic variation of metallic binder phase content originates in the layer by layer deposition of the powder during printing of the green body. It has been found that a period of 40-140 ⁇ m is suitable to achieve a dense and pore free cermet or cemented carbide with hard and wear resistant properties.
  • ceramic is herein intended to denote a material comprising hard constituents in a metallic binder phase, wherein the hard constituents comprise carbides or carbonitrides of one or more of Ta, Ti, Nb, Cr, Hf, V, Mo and Zr, such as TiN, TiC and/or TiCN.
  • cemented carbide is herein intended to denote a material comprising hard constituents in a metallic binder phase, wherein the hard constituents comprise WC grains.
  • the hard constituents can also comprise carbides or carbonitrides of one or more of Ta, Ti, Nb, Cr, Hf, V, Mo and Zr, such as TiN, TiC and/or TiCN.
  • the metallic binder phase in the cermet or in the cemented carbide is a metal or a metallic alloy, and the metal can for example be selected from Cr, Mo, Fe, Co or Ni alone or in any combination.
  • the metallic binder phase comprises a combination of Co, Ni and Fe, a combination of Co and Ni, or only Co.
  • the metallic binder phase can comprise other suitable metals as known to the skilled person.
  • the particle sizes distribution is herein presented by D10, D50 and D90 values.
  • the D50 the median, is defined as the particle diameter where half of the population has a size smaller than this value.
  • 90 percent of the distribution is smaller than the D90 value, and 10 percent of the population is smaller than the D10 value.
  • Powders of Co, Cr and WC were mixed to form a cemented carbide raw powder. Also PEG was added to this raw powder.
  • the spray dried granules were then pre-sintered to remove the PEG but keep a residual porosity in the pre-sintered granules.
  • the pre-sintering was performed at 1230°C for 1 hour.
  • the pre-sintering resulted in a fragile cake of pre-sintered granules, i.e. of porous cemented carbide particles.
  • the cake was breakable by hand, see Fig. 3 .
  • the porosity of the particles was analyzed by studying a through-cut of several particles. Particles were embedded in bakelite and polished and an image analysis was made using ImageJ at 1000x magnification. An example, powder B4, is shown in Fig. 4 .
  • the powder of porous cemented carbide particles was then milled in a 30 liter ball mill for 4 hours. 50-100 kg cemented carbide cylpebs were used. In this milling step a relatively high fraction of particles which are ⁇ 10 ⁇ m in diameter was formed. The amount of small fraction can for example be adjusted by tuning in the milling time.
  • the Co content and the Cr content were studied in ICP-MS or XRF. The results are presented in Table 1.
  • the cemented carbide powders also comprise WC in the amount adding up to 100% from the Co and Cr values in the Table 1.
  • Table 1. Powders Powder Co (wt%) Cr (wt%) D10 ( ⁇ m) D50 ( ⁇ m) D90 ( ⁇ m) Vol% ⁇ 10 ⁇ m (vol%) Powder porosity (vol%) A1 12.79 0.58 2.2 13 29 41 15 A2 12.79 0.58 3.2 14 25.5 32 15 A3 * 12.79 0.58 5.5 20 35 20 15 A4 12.59 0.57 2.0 11.3 23 44.5 20 B1 9.76 0.44 1.5 7.6 17 65 19 B2 9.76 0.44 2.2 11 24 43 19 B3 9.76 0.44 2.2 12 24.5 41 19 B4 9.76 0.44 1.6 10.3 22.4 49 22 * not in accordance with the invention
  • Printing was performed in a binder jetting printing machine with a layer thickness during printing of 100 ⁇ m.
  • "ExOne X1-lab” was used for samples A1S, A2S, A3S, A1SSH, A2SSH, A3SSH, B1SSH, B2SSH, B1S, B2S and "ExOne Innovent" for samples B3S, A4SH, B3SSH, B4SH.
  • Saturation during printing was between 90-97%.
  • the saturation of printing binder is defined as the percent of the void volume that is filled with printing binder at a specified powder packing density (here the powder packing density is set to 60%).
  • a higher saturation is needed when printing with a powder comprising a larger fraction of porous particles as compared to a lower fraction of porous particles.
  • Water based printing ink X1-LabTM Aqueous Binder (7110001CL) was used as printing binder. During the printing the sequence for each layer was as follows: a 100 ⁇ m layer of the powder was spread over the bed, printing binder was spread in a pattern as defined in a CAD model, followed by drying of the printing binder to remove the solvent of the printing binder. This was repeated until the full height of the green body was printed. Thereafter curing was done for 8 hours at 195 °C in argon atmosphere. Depowdering was done manually using a small brush and pressurized air.
  • the printed and cured green bodies were subsequently sintered to provide sintered cemented carbide samples (bodies).
  • the sintering was done at Y-coated graphite trays in a DMK80 sintering furnace.
  • a first sintering process the bodies were subjected to a debinding step where the temperature was increased from room temperature up to 550°C in a sintering chamber with a H 2 flow of 500 l/hour. This was followed by a vacuum step where the temperature was increased from 550°C to 1380°C where it was hold for 30 minutes. Thereafter the temperature was increased to 1410°C where it was hold for one hour. Thereafter the chamber was cooled down and the sintered samples removed from the chamber. Samples treated with this process are named *S, for example A1S. The results are presented in Table 2.
  • Samples A1SSH, A4SH and B1SSH was classified A00B00C00.
  • both the porosity and the amount of ⁇ 10 ⁇ m particles is important to achieve a dense and pore free 3D printed cemented carbide.
  • the binder phase content did vary periodically in the 3D printed bodies. This was studied in detail with EDS and WDS line scans with a JEOL JXA-8530F microprobe. The lines were measured perpendicular to the direction of the printed layers.
  • the instrument settings and WDS crystals used for each analyzed element can be seen in Table 4 and 5.
  • Table 4. EPMA setting for line analysis Line length 1400 ⁇ m Line width 200 ⁇ m Acceleration voltage 15 keV Probe current 50 nA Dwell time 500 ms Step width 3.5 ⁇ m Scan type Stage scan Table 5. Measured elements and WDS-crystals used Element Crystal W PETJ Co LIFH C LDE6H Cr LIFH
  • FIG. 1 shows an example of a typical Co variation
  • Fig. 2 shows an example of a typical Co variation
  • the average binder phase content as an average of 15 adjacent periods, showed a difference of 17 %, 17 % and 16 % from the average binder phase content in the body for samples A1SSH, A2SSH and B2SSH, respectively.
  • Figure 5 shows a through cut of the sample A1S.

Claims (13)

  1. Poudre destinée à une impression tridimensionnelle d'un corps de carbure cémenté ou de cermet, ladite poudre étant constituée de particules de carbure cémenté et/ou de cermet présentant un D90 de 15 à 35 µm, où le D90 est mesuré par diffraction laser, et où la porosité moyenne des particules de cermet et/ou de carbure cémenté d'un diamètre de ≥ 20 µm va de 10 à 40 % en volume, où la porosité est mesurée comme indiqué dans la description, et où de 30 à 70 % en volume des particules présentent un diamètre < 10 µm.
  2. Poudre selon la revendication 1, où le D50 des particules de carbure cémenté et/ou de cermet va de 5 à 20 µm, où le D50 est mesuré par diffraction laser.
  3. Poudre selon la revendication 1 ou 2, où le D10 des particules de carbure cémenté et/ou de cermet va de 1 à 5 µm, où le D10 est mesuré par diffraction laser.
  4. Poudre selon l'une quelconque des revendications précédentes, où la distribution de taille de particules des particules de carbure cémenté et/ou de cermet dans la poudre est unimodale.
  5. Poudre selon l'une quelconque des revendications précédentes, où lesdites particules de cermet et/ou de carbure cémenté comprennent une phase de liant métallique et où la teneur moyenne de phase de liant métallique dans la poudre va de 8 à 14 % en poids.
  6. Poudre selon l'une quelconque des revendications précédentes, où lesdites particules de cermet et/ou de carbure cémenté comprennent une phase de liant métallique et ladite phase de liant métallique comprend du Co.
  7. Procédé de fabrication d'un corps de cermet ou de carbure cémenté imprimé en 3D, ledit procédé comprenant les étapes consistant à :
    - mélanger une poudre brute de cermet ou de carbure cémenté et un liant organique
    - sécher par atomisation ladite poudre brute et former ainsi une poudre brute en granules,
    - pré-fritter ladite poudre brute séchée par atomisation en éliminant ledit liant organique et former ainsi une poudre en granules pré-frittée avec une porosité moyenne des particules de cermet et/ou de carbure cémenté d'un diamètre de ≥ 20 µm allant de 10 à 40 % en volume, où la porosité est mesurée comme indiqué dans la description,
    - broyer ladite poudre en granules pré-frittée jusqu'à ce que 30 à 70 % en volume des particules présentent un diamètre < 10 µm et former ainsi une poudre
    - imprimer en 3D un corps en utilisant ladite poudre et un liant d'impression et former ainsi un corps cru de cermet ou de carbure cémenté imprimé en 3D,
    - fritter ledit corps cru et former ainsi un corps de cermet ou de carbure cémenté imprimé en 3D.
  8. Procédé selon la revendication 7, comprenant en outre, après l'impression 3D et avant le frittage, les étapes consistant à :
    - durcir le corps imprimé en 3D dans une atmosphère inerte à 150-230 °C, et
    - dépoudrer le corps imprimé en 3D afin de retirer les particules libres des surfaces du corps.
  9. Procédé selon la revendication 7 ou 8, dans lequel l'étape de frittage comprend une étape de déliantage, où le liant d'impression est brûlé.
  10. Procédé selon l'une quelconque des revendications 7 à 9, dans lequel la poudre séchée par atomisation est tamisée avant l'étape de pré-frittage, de préférence tamisée de sorte à éliminer les particules de diamètre supérieur à 42 µm.
  11. Procédé selon l'une quelconque des revendications 7 à 10, où le procédé comprend en outre, après l'étape de frittage ou de manière intégrée à cette dernière, une étape de frittage-pressage isostatique à chaud (HIP) du corps de cermet ou de carbure cémenté.
  12. Procédé selon l'une quelconque des revendications 7 à 11, dans lequel l'impression tridimensionnelle est une impression par jet de liant.
  13. Procédé selon l'une quelconque des revendications 7 à 12, dans lequel le corps est un outil de coupe pour découpe de métal ou un outil de coupe pour application minière ou une pièce d'usure.
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US11104979B2 (en) 2021-08-31
IL262284B2 (en) 2023-10-01
KR20180136466A (ko) 2018-12-24
JP2019513901A (ja) 2019-05-30
IL262285A (en) 2018-11-29
JP2019513900A (ja) 2019-05-30
EP3442729A1 (fr) 2019-02-20
IL262285B1 (en) 2023-09-01
CN109311091A (zh) 2019-02-05
IL262284A (en) 2018-11-29
EP3442728A1 (fr) 2019-02-20
KR102269976B1 (ko) 2021-06-25
US20190161837A1 (en) 2019-05-30
JP6933662B2 (ja) 2021-09-08
CN108883467A (zh) 2018-11-23
EP3442729B1 (fr) 2022-02-23
KR20180136465A (ko) 2018-12-24
CN108883467B (zh) 2021-02-02
IL262284B (en) 2022-12-01
CN109311091B (zh) 2021-01-29
JP6861728B2 (ja) 2021-04-21
US11085106B2 (en) 2021-08-10
US20190211424A1 (en) 2019-07-11
IL262285B2 (en) 2024-01-01

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